Substituted methylene pyrazolinones and the herbicidal use thereof

ABSTRACT

The present invention provides thiochroman- and dihydrobenzothiophene-substituted methylene compounds of formula I.                    
     Further provided are compositions and methods utilizing said formula I compounds for the control of undesirable plant species.

This application claims the benefit under 35 U.S.A 119(e) of provisional application 60/186,103 filed Mar. 1, 2000.

BACKGROUND OF THE INVENTION

Weeds cause tremendous global economic losses by reducing crop yields and lowering crop quality. Worldwide, agronomic crops must compete with a vast variety of weed species. Although there are a number of commercial herbicides available, crop safety and efficacy over a broad spectrum of weed species remain challenges in modern agronomic practice. Accordingly there is an ongoing need to discover and develope more crop-selective and broader spectrum herbicidal agents.

Thiochroman- and dihydrobenzothiophene-hydroxypyrazole derivatives and their herbicidal use are described in U.S. Pat. No. 5,607,898 and WO 97/08164. However, thiochroman and dihydrobenzothiophene substituted methylene pyrazolinone compounds and their use as broad-spectrum, crop-selective herbicides are not described therein.

Therefore, it is an object of this invention to provide highly effective broad spectrum herbicidal methylene pyrazolinone compounds.

It is also an object of this invention to provide a method for the control of a broad spectrum of undesirable plant species.

It is a further object of this invention to provide a method for the selective control of undesirable plant species in the presence of a crop.

These and other objects and features of the invention will become more apparent from the detailed description thereof set forth hereinbelow.

SUMMARY OF THE INVENTION

The present invention provides thiochroman-and dihydrobenzothiophene-substituted methylene pyrazolinone compounds of formula I

wherein

m is zero or 1;

R₁, R₂, R₃ and R₄ are each independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl;

R₅ is C₁-C₃ alkyl, C₃-C₄ alkenyl or C₃-C₄ haloalkenyl;

R₆ is H, halogen, CN, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₁-C₄ alkoxyalkyl or C₁-C₄ alkoxycarbonyl;

X is CR₇R₈, CHOR₉, C═NOR₁₀, C═NNR₁₆R₁₇, C═O or C(OR₉)₂;

R₇ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R₈ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl or C₁-C₄ alkoxyalkyl;

R₉ and R₁₀ are each independently H or C₁-C₆ alkyl optionally substituted with one or more C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl or C₃-C₆ cycloalkyl groups;

Y is O, S, SO or SO₂;

Z is H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;

p is an integer of 1, 2 or 3;

G is OR₁₁, OCH₂COR₁₁, SCH₂COR₁₁, OCN₂CSR₁₁, SCH₂CSR₁₁, OCOR₁₁, SCOR₁₁, OCSR₁₁, SCSR₁₁, S(O)_(n)R₁₂, NR₁₃R₁₄, P(O) (OR₁₅)₂, halogen, CN, SCN,

n is zero, 1 or 2;

R₁₁ and R₁₂ are each independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ haloalkynyl, C₁-C₆ alkoxyalkyl, benzyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups or phenyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups;

R₁₃ and R₁₄ are each independently H, C₁-C₆ alkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl, or R₁₃ and R₁₄ may be taken together with the atom to which they are attached to represent a four- to seven-membered ring optionally interrupted by oxygen, sulfur, or nitrogen and optionally substituted with one to three halogen or C₁-C₆ alkyl groups;

R₁₅ is C₁-C₆ alkyl;

R₁₆ is H or C₁-C₆ alkyl;

R₁₇ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, COR₁₈ or phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups, or R₁₆ and R₁₇ may be taken together to represent ═C(C₁-C₃ alkyl)₂;

R₁₈ is phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups, or a 5-to 6-membered aromatic heterocyclic ring optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups;

M is a transition metal or an alkaline-earth metal; and

q is an integer of 1, 2 or 3; or the geometric or optically active isomers thereof.

The present invention also provides herbicidal compositions and methods and a process to prepare a compound of formula I.

DETAILED DESCRIPTION OF THE INVENTION

Good pest management practice requires new herbicidal agents which demonstrate efficacy toward a broad spectrum of undesirable monocotyledenous and dicotyledenous plant species and preferably also demonstrate crop safety.

Surprisingly it has now been found that thiochroman and dihydrobenzothiophene derivatives of methylene pyrazolinone compounds of formula I demonstrate a broad spectrum of weed control along with acceptable or good crop safety. In particular said methylene pyrazolinone formula I compounds are surprisingly safe in cereal crops such as corn, wheat, rice, or the like, preferably corn.

The compounds of the invention have the structural formula I

wherein R₁, R₂, R₃, R₄, R₅, R₆, G, X, Y, Z, m and p, are as defined hereinabove for formula I.

Preferred methylene pyrazolinone compounds of the invention are those compounds of formula I wherein

R₁, R₂, R₃ and R₄ are each independently H or C₁-C₄ alkyl;

R₅ is C₁-C₃ alkyl;

R₆ is H or C₁-C₄ alkyl;

X is CR₇R₈ or C═NOR₁₀;

R₇ and R₈ are each independently H or C₁-C₄ alkyl;

R₁₀ is H or C₁-C₆ alkyl;

Y is SO₂;

Z is H, halogen or C₁-C₄ alkyl;

G is OR₁₁, S(O)_(n)R₁₂, NR₁₃R₁₄,

n is zero, 1 or 2;

R₁₁ and R₁₂ are each independently C₁-C₆ alkyl or phenyl optionally substituted with one to three halogen, C₁-C₆alky, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl groups; and

R₁₃ and R₁₄ are each independently H or phenyl optionally substituted with one to three halogen, C₁-C₆alkyl, C₁-C₆alkoxy or C₁-C₆haloalkyl groups.

More preferred compounds of the invention are those compounds of formula I wherein

m is zero;

R₁ and R₂ are H;

R₅ is C₁-C₃ alkyl;

R₆ is H;

X is CR₇R₈;

R₇ and R₈ are each independently C₁-C₄ alkyl;

Y is SO₂;

Z is C₁-C₄ alkyl;

p is 1 or 2;

G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2;

R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkyl groups; and

R₁₂ is C₁-C₆ alkyl, C₁-C₃alkoxyalkyl or C₁-C₃haloalkyl.

Particularly preferred compounds of the invention are those compounds of formula I wherein

m is 1;

R₁, R₂, R₃ and R₄ are H;

R₅ is C₁-C₃ alkyl;

R₆ is H;

X is C═NOR₁₀;

R₁₀ is C₁-C₆ alkyl;

Z is C₁-C₄ alkyl;

p is 1 or 2;

G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2;

R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl, C₁-C₃ alkoxy, or C₁-C₃ haloalkyl groups; and

R₁₂ is C₁-C₆ alkyl, C₁-C₃alkoxyalkyl or C₁-C₃haloalkyl.

The term halogen as used in the specification and claims designates chlorine, fluorine, bromine or iodine. The term haloalkyl designates an alkyl group, C_(n)H_(2n+1) which may contain from one halogen atom to 2n+1 halogen atoms. Similarly, the term haloalkoxy designates a OC_(n)H_(2n+1) group which may contain from one to 2n+1 halogen atoms. Haloalkenyl designates an alkenyl group C_(n)H_(2n) which may contain from one to 2n halogen atoms. In each instance the halogen atoms may be the same or different. Similarly, the term C₁-C₃ alkoxyalkyl designates a C₁-C₆ alkyl group substituted with one or more C₁-C₃ alkoxy groups which may be the same or different.

The term transition metal as used in the specification and claims designates zinc, copper, iron, manganese, titanium, nickel, or any of the commonly occurring transition elements listed in Groups IB through VIIIB on the periodic chart. Similarly, the term alkaline-earth metal designates magnesium, calcium, strontium, barium or any of the commonly occurring alkaline-earth elements listed in Group IIA on the periodic chart.

Compounds of formula I may exist in enolic tautomeric forms that may give rise to geometric isomers around the enolic double bond. The wavy lines in structural formula I represent the interchangeability of the G moiety and the bicyclic structure around the methine carbon, i.e. the E isomeric or the Z isomeric configuration. Further, structural formula I may include one or more assymetric carbon atoms, giving rise to stereoisomeric forms. All such geometric and stereoisomeric forms of the compound of formula I are embraced by the present invention.

Among the formula I compounds of the invention which are particularly effective herbicidal agents are:

1-Ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide;

1-Ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide;

1-Ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide;

1-Ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime}, S,S-dioxide;

4,4′-[(Z,Z)-Dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide;

4,4′-[(E,Z)-Dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide;

4-[(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo [b] thien-5-yl)(propylthio)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide;

4-{(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo [b] thien-5-yl)[(m-trifluoromethyl)anilino]methylene}-1-methyl-2-pyrazolin-5-one S,S-dioxide;

4-[(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)(p-methoxyphenoxy)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide; or the like.

Formula I compounds wherein G is OR₁₁ or SR₁₂ may be prepared by reacting the chloro compound of formula Ia with a hydroxy compound R₁₁OH or a thiol R₁₂SH, respectively, in the presence of a base. The reaction is shown in flow diagram I.

FLOW DIAGRAM I

The chloro compound of formula Ia may be prepared by reacting an alkylsulfonate of formula II with an aroyl chloride ArCOCl as shown in Flow Diagram II.

FLOW DIAGRAM II

Alternatively, the compound of formula I wherein G is SR₁₂ may be prepared by the conversion of a ketone of formula III to a thioketone of formula IV with Lawesson's reagent, and alkylating said thioketone with an alkylating agent R₁₂Z₁ wherein Z₁ is Cl, Br or I, in the presence of a base. Compounds of formula I wherein G is SR₁₂ may be oxidized to the corresponding sulfoxide or sulfone derivative with one or two molar equivalents of an oxidant such as m-chloroperbenzoic acid. The reactions are shown in Flow Diagram III.

FLOW DIAGRAM III

Compounds of formula II and formula III and methods for their preparation are described in U.S. Pat. No. 5,607,898 and WO 97/08164.

The compound of formula I wherein G is

may be prepared by direct oxidation of a thioketone of formula IV as shown in Flow Diagram IV.

FLOW DIAGRAM IV

Compounds of formula I wherein G is

may be prepared by treatment of a thione of formula IV with a transition metal or alkaline-earth metal salt M^(+q)(X₁)_(q), wherein X₁ is a halide, acetate or nitrate anion, in the presence of an acid or a base as shown in Flow Diagram V.

FLOW DIAGRAM V

Compound I wherein G is NR₁₃R₁₄ may be prepared by reacting the chloro compound of formula Ia with an amine HNR₁₃R₁₄, in the presence of a base, as depicted in Flow Diagram VI.

FLOW DIAGRAM VI

Compound I wherein G is P(O) (OR₁₅)₂ may be prepared by treating chloro compound Ia with a phosphite P(OR₁₅)₃ as depicted in Flow Diagram VII.

FLOW DIAGRAM VII

Advantageously, it has been found that the formula I compounds of the invention are particularly useful for the control of undesirable monocotyledenous and dicotyledenous plant species. Surprisingly, the compounds of this invention demonstrate selective weed control in cereal crops such as corn, wheat, rice, or the like preferably corn or rice.

In actual practice, compounds of the invention may be applied to the foliage of undesirable plant species or to the soil or water containing seeds or other propagating organs thereof in the form of a solid or liquid herbicidal composition. Compositions of the invention comprise a herbicidally effective amount of the compound of formula I dispersed or dissolved in an agronomically acceptable inert solid or liquid carrier. Herbicidally effective amounts may vary according to the prevailing conditions such as weed pressure, crop species, application timing, soil conditions, weather conditions and the like. In general, amounts sufficient to selectively control weeds are obtained when the formula I compound is applied at rates of about 0.001 kg/ha to 10.0 kg/ha, preferably about 0.003 to 0.50 kg/ha, more preferably about 0.006 to 0.20 kg/ha.

The composition of the present invention may take the form of an emulsifiable concentrate, a concentrated emulsion, a microemulsion, a wettable powder, a soluble granule, a suspension concentrate, a flowable concentrate or any convenient conventional form useful for herbicide application.

The composition of the invention may be applied in combination with other herbicides such as dinitroanlines, for example trifluralin, pendimethalin or the like; triazines, for example atrazine, cyanazine, metribuzin or the like; AHAS inhibitors for example imidazolinones, sulfonyl ureas or the like; protox inhibitors; or any of the commonly employed, commercially available herbicidal agents. Said combination may be applied sequentially or concurrently as a tank-mix or co-formulation. Compositions of the invention embrace compounds of formula I alone or in combination with a second herbicide as active ingredient.

In order to facilitate a further understanding of the invention, the following examples are presented to illustrate more specific details thereof. The invention is not to be limited thereby except as defined in the claims. The terms ¹HNMR and ¹³CNMR designate proton and carbon NMR respectively, and the terms IR and MS designate infrared spectrometry and mass spectroscopy, respectively.

EXAMPLE 1 Preparation of 4-[(Z)-Chloro-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide

A solution of 2,3-dihydro-5-[(5-hydroxy-1-methylpyrazol-4-yl)carbonyl]-3-3-4-trimethylbenzo[b]thiophene propanesulfonate 1,1-dioxide (0.160 g, 0.36 mmol) in methylene chloride is treated with a solution of (3,3,4-trimethylbenzo[b]thien-5-yl)-5-carboxylic acid chloride in methylene chloride, heated in a sealed pressure vial at 60-70° C. for 24 hr, cooled, diluted with methylene chloride and chromatographed on silica gel with methylene chloride to give a crude solid. Crystallization of the solid with methanol affords the title compound as a yellow solid (0.100 g, 78%, mp 195-197° C.), characterized by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 2 Preparation of 4-[(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)(dimethylamino)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide

Dimethylamine gas is bubbled through a stirred solution of 4-[(Z)-chloro(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide (0.100 g, 0.280 mmol) in dioxane at room temperature for two hours. The solution is concentrated in vacuo to give a residue. The residue is taken up in methylene chloride, washed successively with cold 10% aqueous sodium carbonate and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give a second residue. This residue is taken up in methylene chloride and chromatographed on silica gel using a gradient elution (methylene chloride/methanol: 100/0 to 98/2) to afford the title compound as a solid (0.064 g, 64%, mp 205-207° C.), identified by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 3 Preparation of 4-[(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo-[b]thien-5-yl)(p-methoxyphenoxy)methylene]-1-methyl-2-pyrazolin-5-one, S,S-dioxide

A mixture of 4-[(Z)-chloro(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide (0.100 g, 28.4 mmol), 4-methoxyphenol (4-MP) (0.040 g, 32.2 mmol) and potassium carbonate (0.045 g, 32.6 mmol) in dry N,N-dimethylformamide is stirred at room temperature for 16 hr, diluted with cold water and extracted with methylene chloride. The combined organic extracts are washed with 10% aqueous sodium carbonate and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give a residue. The residue is chromatographed on silica gel with ethyl acetate-hexanes to afford the title compound as a light yellow semi-solid, 0.040g (32% yield) characterized by ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 4 Preparation of 6-[(1-Ethyl-5-hydroxypyrazol-4-yl)thiocarbonyl]-5-methylthiochroman-4-one (E)-O-methyloxime, 1,1-dioxide

A stirred suspension of the 4-(O-methyloxime) of 6-[(1-ethyl-5-hydroxypyrazol-4-yl)carbonyl]-2,3-dihydro-5-methyl-4H-1-benzothiopyran-4-one, 1,1-dioxide (50.0 g, 0.132 mol) in dimethoxyethane, under nitrogen, is treated with Lawesson's Reagent (53.6 g, 0.132 mol), heated at 65-70° C. for a period of 15 h [during this period, additional Lawesson's Reagent is added (39.5 g, 0.098 mol)], cooled to room temperature and filtered. The filtrate is concentrated in vacuo to give a syrup. The syrup is diluted with diethyl ether, washed sequentially with water and brine, dried over sodium sulfate and concentrated in vacuo to give a second syrup. The second syrup is dissolved in methylene chloride and chromatographed on silica gel using a gradient elution (methylene chloride/diethyl ether: 100/0 to 90/10) to give the title compound as a golden yellow solid, mp 92°-97° C., 24.1 g, (46.1% yield), identified by IR, ¹HNMR, ¹³CNMR and MS analyses. Quantitative NMR analysis indicates a product purity of 97.7% with the ratio of oxime isomers (E/Z: 95/5) unchanged from the ratio found in the starting material.

EXAMPLE 5 Preparation of 2,3-Dihydro-3,3,4-trimethylbenzo[b]thien-5-yl 5-hydroxy-1-methylpyrazol-4-yl thione 1,1-dioxide

Using essentially the same procedure as described above in example 4 and employing on 2,3-dihydro-5-[(5-hydroxy-1-methylpyrazol-4-yl)carbonyl]-3,3,4-trimethyl-benzo[b]thiophene 1,1-dioxide, affords the title product as a light yellow powder, mp 214-216° C., characterized by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 6 Preparation of 4-Methoximino-5-methyl-6-(1-ethyl-5-hydroxypyrazol-4-yl)thiocarbonylthiochroman-1,1-dioxide, zinc (+2) chelate

A mixture of finely ground zinc acetate dihydrate (0.233 g, 1.067 mmol) in glacial acetic acid is treated with acetic anhydride (0.217 g, 2.13 mmol) and heated to reflux briefly to give a suspension. This suspension is added, while hot, to a solution of 6-[(1-ethyl-5-hydroxypyrazol-4-yl)thiocarbonyl]-5-methylthiochroman-4-one (E)-O-methyloxime, 1,1-dioxide (0.84 g, 2.13 mmol) in glacial acetic acid. The reaction mixture is heated to reflux for five minutes, cooled and filtered. The filtercake is washed with acetic acid and air-dried to afford the title compound as a bright orange yellow solid, 0.25 g (27% yield), mp>255° C., identified by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 7 Preparation of 4,4′-[(Z,Z)-Dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′,-tetraoxide, 80:20 mixture with 4,4′-[(E,Z)-dithiobis[(2,3-dihydro-3,3,4-trimethyl-benzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide

A mixture of 2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl 5-hydroxy-1-methylpyrazol-4-yl thione 1,1-dioxide(0.15 g, 0.428 mmol), N-bromosuccinimide (NBS) (0.0914 g, 0.514 mmol), and dibenzoyl peroxide (0.020 g, 0.041 mmol) in carbon tetrachloride is refluxed for 15 minutes, cooled to room temperature, washed with water and brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give a syrup. The residual yellow-orange syrup is chromatographed on silica gel using a gradient elution (methylene chloride/diethyl ether: 100/0 to 90/10) to afford the title product mixture as a light yellow syrup, 0.11 g (73% yield), identified by NMR analysis to be of an 80:20 mixture of the (Z,Z):(Z:E) isomers.

EXAMPLE 8 Preparation of 1-Ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide (Example 8a) and 1-Ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propythio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide (Example 8b)

A solution of 6-[(1-ethyl-5-hydroxypyrazol-4-yl)thiocarbonyl]-5-methylthiochroman-4-one (E)-O-methyloxime, 1,1-dioxide (1.00 g, 2.54 mmol) and triethylamine (Et₃N) (0.27 g, 2.67 mmol) in methylene chloride at −5° C. is treated with n-propyl iodide (0.45 g, 2.67 mmol), stirred overnight at room temperature, poured onto ice, acidified with 10% hydrochloric acid and diluted with methylene chloride. The phases are separated. The organic phase is washed sequentially with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford a residue. Gradient elution chromatography on silica gel (methylene chloride/diethyl ether: 100/0 to 90/10) affords two yellow solid fractions. Recrystallization of each from methylene chloride/hexanes afforded the title product E,E-isomer (designated 8a), 0.19 g(17% Yield) mp 173-176° C. and the title product Z,E-isomer (designated 8b), 0.41 g(37% yield) mp 195-196° C. Each isomeric product is characterized by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 9 Preparation of 4-{(Z)-(2,3-Dihydro-3,3,4-trimethylbenzo-[b]thien-5-yl)(propylthio)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide

Following essentially the same procedure described above in Example 8 and employing 2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl 5-hydroxy-1-methylpyrazol-4-yl thione 1,1-dioxide affords the title product, mp 185.5-187° C. (10% yield), identified by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 10 Prepration of Substituted Methylene Pyrazolinone Compounds

Using essentially the same procedures described hereinabove and employing the appropriate substrate and alkylating agent the following compounds are obtained.

R₅ R₇ R₈ R₁₂ Z mp ° C. CH₃ CH₃ CH₃ CH₂CH═CH₂ CH₃ 230-231 CH₃ CH₃ CH₃ CH₂C≡CH CH₃ 198-205 CH₃ CH₃ CH₃ CH₂C₆H₅ CH₃ 145-203

EXAMPLE 11 Preparation of 1-Ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl) (propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime, S,S-dioxide, 62:38 mixture with 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl) (propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide

A solution of 1-ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl) (propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide and 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl) (propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide (0.20 g, 0.469 mmol) in methylene chloride at room temperature is treated dropwise with a solution of 57% m-chloroperbenzoic acid (m-CPBA) (0.24 g, 1.38 mmol) in methylene chloride, stirred for 4.5 hours, cooled to room temperature, washed sequentially with 10% aqueous sodium bicarbonate, water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford a residue. The residue is chromatographed on silica gel using methylene chloride/ether to give the title product as a 62:38 E:Z isomer mixture, mp 84-89° C., 0.16 g, (74% yield), identified by IR, ¹HNMR, ¹³CNMR and mass spectral analyses.

EXAMPLE 12 Postemergence Herbicidal Evaluation Of Test Compounds

The postemergence herbicidal activity of the compounds of the present invention is evaluated by the following tests. Seedling plants are grown in jiffy flats for about two weeks. The test compounds are dispersed in 80/20 (v/v) acetone/water mixtures containing 1.0% SUN-IT®II, a methylated seed oil, in sufficient quantities to provide the equivalent of about 0.006 kg/ha to 0.800 kg/ha of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in accordance with conventional greenhouse procedures. Approximately two to three weeks after treatment, the seedling plants are examined and rated according to the rating system set forth below. Where more than one test is involved for a given compound, the data are averaged. The results are shown in Table I.

HERBICIDE RATING SCALE % Control Rating Compared to Check 9 100 8 91-99 7 80-90 6 65-79 5 45-64 4 30-44 3 16-29 2  6-15 1 1-5 0 0

PLANT SPECIES Column Heading Common Name Scientific Name ABUTH Velvetleaf Abutilon theophrasti, Medic. AMBEL Ragweed Ambrosia artemisifolia, L. CHEAL Lambsquarters Chenopodium album, L. IPOSS Morningglory spp. Ipomoea spp. ECHCG Barnyardgrass Echinochloa crus-galli, (L.) Beau PANDI Panicum, Fall Panicum dichotomiflorum, Michx SETVI Foxtail, Green Setaria viridis, (L.) Beau GOSHI Cotton Gossypium hirsutum, L. ORYSAT Rice, Tebonnet Oryza sativa, (L.) Tebonnet ZEAMX Corn, Field Zea mays, L. (Sammel-Bezeichnung)

TABLE I Postemergence Herbicidal Evaluation Ex. Rate No. (kg/ha) ABUTH AMBEL CHEAL IPOSS ECHCG PANDI SETVI GOSHI ORYSAT ZEAMX 2 0.1000 0.0 0.0 0.0 0.0 0.0 0.0 2 0.0500 0.0 0.0 0.0 0.0 0.0 0.0 2 0.0250 0.0 0.0 0.0 0.0 0.0 0.0 2 0.0125 0.0 0.0 0.0 0.0 0.0 0.0 3 0.1000 7.0 7.0 9.0 6.0 7.0 2.0 3 0.0500 7.0 7.0 8.0 4.0 5.0 0.0 3 0.0250 4.0 4.0 6.0 3.0 3.0 0.0 3 0.0125 2.0 2.0 6.0 2.0 1.0 0.0 7 0.1000 7.0 9.0 2.0 9.0 9.0 9.0 7.0 2.0 7 0.0500 5.0 9.0 2.0 8.0 7.0 9.0 7.0 0.0 7 0.0250 4.0 7.0 1.0 7.0 3.0 7.0 6.0 0.0 7 0.0125 3.0 4.0 1.0 7.0 5.0 7.0 3.5 0.0 8a 0.8000 6.0 8.0 9.0 4.0 9.0 9.0 9.0 6.0 5.0 0.5 8a 0.4000 8.0 7.0 9.0 2.0 9.0 6.0 8.0 3.0 5.0 0.0 8a 0.2000 2.0 6.0 9.0 0.0 8.0 7.0 5.0 0.0 1.5 0.0 8a 0.1000 1.0 3.0 9.0 0.0 8.0 6.0 4.0 0.0 0.7 0.0 8a 0.0500 0.0 2.0 7.0 0.0 8.0 3.0 1.0 0.0 0.0 0.0 8b 0.8000 6.0 7.0 9.0 0.0 9.0 6.0 9.0 4.5 3.5 0.0 8b 0.4000 5.0 7.0 9.0 0.0 9.0 7.0 9.0 4.0 1.5 0.0 8b 0.2000 5.0 7.0 8.0 0.0 8.0 7.0 4.0 0.0 3.5 0.0 8b 0.1000 0.0 5.0 8.0 0.0 8.0 6.0 3.5 0.0 1.7 0.0 8b 0.0500 1.0 0.0 7.0 0.0 6.5 2.0 3.5 0.0 1.0 0.0 10 0.8000 7.0 9.0 9.0 5.0 8.0 8.0 9.0 6.5 7.0 6.0 10 0.4000 8.0 8.0 9.0 5.0 9.0 8.0 9.0 6.5 7.0 6.0 10 0.2000 8.0 8.0 9.0 3.0 8.0 8.0 9.0 6.5 7.5 3.5 10 0.1000 6.0 8.0 9.0 3.0 9.0 7.0 9.0 5.0 7.0 0.5 10 0.0500 6.0 8.0 9.0 5.0 8.0 8.0 9.0 5.0 5.5 0.0

EXAMPLE 13 Preemergence Herbicidal Evaluation Of Test Compounds

The preemergence herbicidal activity of the test compounds of the present invention is exemplified by the following tests in which the seeds of a variety of monocotyledonous and dicotyledonous plants are separately mixed with potting soil and planted on top of approximately one inch of soil in separate pint cups. After planting, the cups are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide the equivalent of about 0.0125 kg/ha to 0.800 kg/ha of test compound per cup. The treated cups are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. Approximately two to four weeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system provided in Example 12. When more than one test is performed for a given compound, the data are averaged. The results are shown in Table II.

TABLE II Preemergence Herbicidal Evaluation Ex. Rate No. (kg/ha) ABUTH AMBEL CHEAL IPOSS ECHCG PANDI SETVI GOSHI ORYSAT ZEAMX 6 0.8000 9.0 9.0 9.0 5.0 8.0 8.0 9.0 7.0 9.0 0.0 6 0.4000 9.0 9.0 9.0 5.0 9.0 8.0 9.0 8.0 9.0 1.0 6 0.2000 9.0 9.0 9.0 6.0 9.0 9.0 9.0 6.0 9.0 0.0 6 0.1000 9.0 8.0 9.0 3.0 9.0 9.0 7.0 1.0 7.0 0.0 6 0.0500 9.0 7.0 9.0 1.0 3.0 6.0 4.0 0.0 4.0 0.0 8a 0.8000 6.0 6.0 9.0 2.0 2.0 8.0 5.0 2.0 3.0 0.0 8a 0.4000 2.0 3.0 9.0 0.0 0.0 5.0 4.0 0.0 0.0 0.0 8b 0.8000 9.0 6.0 9.0 0.0 0.0 7.0 3.0 0.0 0.0 0.0 8b 0.4000 0.0 3.0 7.0 0.0 0.0 7.0 0.0 0.0 0.0 0.0 8b 0.2000 0.0 0.0 6.0 0.0 0.0 2.0 3.0 0.0 0.0 0.0 10 0.8000 9.0 9.0 9.0 7.0 9.0 8.0 9.0 7.0 8.0 6.0 10 0.4000 9.0 9.0 8.0 3.0 8.0 8.0 9.0 6.0 0.0 10 0.2000 8.0 9.0 9.0 4.0 7.0 8.0 9.0 6.0 7.0 0.0 10 0.1000 9.0 9.0 9.0 7.0 8.0 7.0 9.0 5.0 8.0 1.0 10 0.0500 9.0 6.0 9.0 2.0 6.0 7.0 8.0 1.0 6.0 0.0 

What is claimed is:
 1. A compound of formula I

wherein m is zero or 1; R_(1,)R_(2,)R₃ and R₄ are each independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl; R₅ is C₁-C₃ alkyl, C₃-C₄ alkenyl or C₃-C₄ haloalkenyl; R₆ is H, halogen, CN, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₁-C₄ alkoxyalkyl or C₁-C₄alkoxycarbonyl; X is CR₇R₈, CHOR₉, C═NNR₁₆R₁₇, C═NOR₁₀, C═O or C(OR₉)₂; R₇ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R₈ is H, C₁-C₄ alkyl, C₂-C₄ alkynyl or C₁-C₄alkoxyalkyl; R₉ and R₁₀ are each, independently H or C₁-C₆ alkyl optionally substituted with one or more C₂-C₆ alkenyl, C₂-C₆ haloalkyl or C₃-C₆ cycloalkyl groups; Y is O, S, SO or SO₂; Z is H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; p is an integer of 1,2 or 3; G is OR₁₁, OCH₂COR₁₁, OCN₂CSR₁₁, SCH₂CSR₁₁, OCOR_(11,) SCOR_(11,) OCSR_(11,) SCSR_(11,) S(O)_(n)R_(12,) NR₁₃R_(14,) P(O)(OR₁₅)₂, halogen, CN,SCN,

n is zero, 1 or 2; R₁₁ and R₁₂ are each independently C₁-C₆ alkyl, C₁-C₆ halo alkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₁-C₆ alkoxyalky, benzyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl groups, or phenyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, or C₁-C₆ haloalkyl groups; R₁₃ and R₁₄ are each independently hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl, or R₁₃ and R₁₄ maybe taken together with the atoms to which they are attached to represent a four -to seven=membered ring optionally interrupted by oxygen, sulfur or nitrogen and optionally substituted with one to three halogen or C₁-C₆ alkyl groups; R₁₅ is C_(1-C) ₆ alkyl; R₁₆ is H or C₁-C₆ alkyl; R₁₇ is H, C_(1 -C) ₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylcarbonyl, COR₁₈ or phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups, or R₁₆ and R₁₇ may be taken together to represent ═C(C₁-C₃ alkyl)₂; R₁₈ is phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups; M is a transition metal or an alkaline-earth metal; and q is an integer of 1,2 or 3; or the geometric or optically active isomers thereof.
 2. The compound according to claim 1 wherein R₁, R₂, R₃ and R₄ are each independently H or C_(1-C) ₄ alkyl; R₅ is C_(1-C) ₃ alkyl; R₆ is H or C_(1-C) ₄ alkyl; X is CR₇R₈ or C═NOR₁₀; R₇ and R₈are each independently H or C₁-C₄ alkyl; R₁₀ is H or C_(1-C) ₆ alkyl; Y is SO₂; Z is H, halogen or C_(1-C) ₄ alkyl; G is OR₁₁, S(O)R₁₂,

R₁₁ and R₁₂ are each independently C_(1-C) ₆ alkyl or phenyl optionally substituted with one to three halogen, C_(1-C) ₆ alkyl, C_(1-C) ₆ alkoxy, or C_(1-C) ₆ haloalkyl groups.
 3. The compound according to claim 2 wherein m is zero; R₁ and R₂ are H; R₅ is C_(1-C) ₃ alkyl; R₆ is H; X is CR₇R₈; R₇ and R₈ are each independently C_(1-C) ₄ alkyl; Z is C_(1-C) ₄ alkyl; p is 1; G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C_(1-C) ₂ alkyl, C_(1-C) ₃ alkoxy, or C_(1-C) ₃ haloalkyl groups; and R₁₂ is C_(1-C) ₆ alkyl.
 4. The compound according to claim 2 wherein m is 1; R₁, R₂, R₃ and R₄ are H; R₅ is C_(1-C) ₃ alkyl; R₆ is H; X is C═NOR₁₀; R₁₀ is C_(1-C) ₆ alkyl; Z is C_(1-C) ₄ alkyl; p is 1; G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C_(1-C) ₂ alkyl, C_(1-C) ₃ alkoxy, or C_(1-C) ₃ haloalkyl groups; and R₁₂ is C_(1-C) ₆ alkyl.
 5. The compound according to claim 1 selected from the group consisting of: 1-ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime}, S,S-dioxide; 4,4′-[(Z,Z)-dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis]1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide; 4,4′-[(E,Z)-dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide; 4-[(Z)-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)(propylthio)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide; 4-{(Z)-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)[(m-trifluoromethyl)anilino]methylene}-1-methyl-2-pyrazolin-5-one S,S-dioxide; and 4-(Z)-(2,3-dihydro-3,3,4-trimethylbenzo [b]thien-5-yl)(p-methoxyphenoxy)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide.
 6. A method for the control of undesirable monocotyledenous and dicotyledenous plants which comprises applying to the foliage of said plants or to the soil or water containing seeds or other propagating organs thereof a herbicidally effective amount of a compound of formula I

wherein R₁ R₂, R₃, R₄, R₅, R₆, G, X, Y, Z, m and p are as defined in claim
 1. 7. The method according to claim 6 having a formula I compound wherein R₁, R₂, R₃ and R₄ are each independently H, or C₁-C₄ alkyl; R₅ is C₁-C₃ alkyl; R₆ is H, or C₁-C₄ alkyl; X is CR₇R₈ or C═NOR₁₀; R₇ and R₈ are each independently H or C₁-C₄ alkyl; R₁₀ is H or C₁-C₆ alkyl; Y is SO₂; Z is H, halogen, or C₁-C₄ alkyl; G is OR₁₁, SO_(n)R₁₂,

R₁₁ and R₁₂ are each independently C₁-C₆ alkyl or phenyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups.
 8. The method according to claim 7 having a formula I compound wherein m is zero; R₁ and R₂ are H; R₅ is C₁-C₃ alkyl; R₆ is H; X is CR₇R₈; R₇ and R₈ are each interdependently C₁-C₄ alkyl; Z is C₁-C₄ alkyl; p is 1; G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkyl groups; and R₁₂ is C₁-C₆ alkyl.
 9. The method according to claim 7 having a formula I compound wherein m is 1; R₁, R₂, R₃ and R₄ are H; R₅ is C₁-C₃ alkyl; R₆ is H; X is C═NOR₁₀; R_(10 is C) ₁-C₆ alkyl; Z is C₁-C₄ alkyl; p is 1; G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkyl groups; and R₁₂ is C₁-C₆ alkyl.
 10. The method according to claim 6 wherein the compound of formula I is selected from the group consisting of: 1-ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylthio)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(E)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime], S,S-dioxide; 1-ethyl-4-[(Z)-(5-methyl-4-oxothiochroman-6-yl)(propylsulfonyl)methylene]-2-pyrazolin-5-one 4′-[(E)-O-methyloxime}, S,S-dioxide; 4,4-[(Z,Z)-dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis]1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide; 4,4′-[(E,Z)-dithiobis[(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)methylidyne]]bis[1-methyl-2-pyrazolin-5-one] S,S,S′,S′-tetraoxide; 4-[(Z)-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)(propylthio)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide; 4-{(Z)-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)[(m-trifluoromethyl)anilino]methylene}-1-methyl-2-pyrazolin-5-one S,S-dioxide; and 4-[(Z)-(2,3-dihydro-3,3,4-trimethylbenzo[b]thien-5-yl)(p-methoxyphenoxy)methylene]-1-methyl-2-pyrazolin-5-one S,S-dioxide.
 11. The method according to claim 6 wherein said undesirable plants are in the presence of a crop plant, crop seed or other crop propagating organ.
 12. The method according to claim 11 wherein said crop is a cereal crop.
 13. The method according to claim 12 wherein the cereal crop is corn or rice.
 14. The method according to claim 6 wherein said formula I compound is applied at a rate of about 0.001 kg/ha to 1.0 kg/ha.
 15. A herbicidal composition which comprises an inert solid or liquid carrier and a herbicidally effective amount of a compound of formula I

wherein R₁, R₂, R₃, R₄, R₅, R₆, G, X, Y, Z, m and p are as defined in claim
 1. 16. The composition according to claim 15 wherein R₁, R₂, R₃ and R₄ are each independently H or C₁-C₄ alkyl; R₅ is C₁-C₃ alkyl; R₆ is H, or C₁-C₄ alkyl; X is CR₇R₈ or C═NOR₁₀; R₇ and R₈ are each independently H or C₁-C₄ alkyl; R₁₀ is H or C₁-C₆ alkyl; Y is SO₂; Z is H, halogen or C₁-C₄ alkyl; G is OR₁₁, SO_(n)R₁₂,

R₁₁ and R₁₂ are each independently C₁-C₆ alkylor phenyl optionally substituted with one to three halogen, C₁-C₆ alkyl C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups.
 17. The composition according to claim 15 wherein m is zero; R₁ and R₂ are H; R₅ is C₁-C₃ alkyl; R₆ is H; X is CR₇R₈; R₇ and R₈ are each independently C₁-C₄ alkyl; Z is C₁-C₄ alkyl; p is 1; G is OR₁₁, S(O)_(n)R₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl C₁-C₃ alkoxy or C₁-C₃ haloalkyl groups; and R₁₂ is C₁-C₆ alkyl.
 18. The composition according to claim 15 wherein m is 1; R₁, R₂, R₃ and R₄ are H; R₅ is C₁-C₃ alkyl; R₆ is H; X is C═NOR₁₀; R₁₀ is C₁-C₆ alkyl; Z is C₁-C₄ alkyl; p is 1; G is OR₁₁, S(O)nR₁₂,

n is zero or 2; R₁₁ is phenyl optionally substituted with one to three halogen, C₁-C₂ alkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkyl groups; and R₁₂ is C₁-C₆ alkyl.
 19. A process for the preparation of a compound of formula I

wherein m is zero or 1; R₁, R₂, R₃ and R₄ are each, independently h, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₂-C₄ alkoxyalkyl; R₅ is C₁-C₃ alkyl, C₃-C₄ alkenyl or C₃-C₄ haloalkenyl; R₆ is H, halogen, CN, C₁-C₄ alkyl, C₂ -C₄ alkenyl, C₁-C₄ alkoxyalkyl or C₁-C₄alkoxycarbonyl; X is CR₇ ₈, CHOR₉, C═NNR₁₆R₁₇, C═NOR₁₀, C═O or C(OR₉)₂; R₇ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R₈ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl or C₁-C₄alkoxyalkyl; R₉ and R₁₀ are each, independently H or C₁-C₆ alkyl optionally substituted with one or more C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl or C₃-C₆ cycloalkyl groups; Y is O, S, SO or SO₂; Z is H, halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; p is an integer of 1,2 or 3; G is OR₁₁, S(O)₇R₁₂, NR₁₃R₁₄, P(O)(OR₁₅)₂ or halogen; n is zero, 1 or 2; R₁₁ and R₁₂ are each independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ haloalkynyl, C₁-C₆ alkoxyalkyl, benzyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups, or phenyl optionally substituted with one to three halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ haloalkyl groups; R₁₃ and R₁₄ are each independently H, C₁-C₆ alkyl, C₃-C₆ alkenyl, C₃-C₆ alkynyl, or when R₁₃ and R₁₄ are taken together with the atoms to which they are attached, they represent a four- to seven- membered ring optionally interrupted by oxygen, sulfur, or nitrogen and optionally substituted with one to three halogen or C₁-C₆ alkyl groups; R₁₅ is C₁-C₆ alkyl; R₁₆ is H or C₁-C₆ alkyl; R₁₇ is H, C₁-C₆ haloalkyl, C₂-C₆ aldoxycarbonyl, C₂-C₆ alkylcarbonyl, COR₁₈ or phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen, CN or NO₂ groups, or R₁₆ and R₁₇ may be taken together to represent ═C(C₁-C₃ alkyl)₂; and R₁₈ is phenyl optionally substituted with one to three C₁-C₃ alkyl, halogen CH or NO₂ groups, which process comprises reacting an aroyl halide with a compound of formula II

wherein R₁, R₂, R₃, R₄, R₅, R₆, X, Y, Z, m and p are as defined above to form a compound of formula I wherein G is halogen; and reacting said compund with at least one molar equivalent of one member selected from the group consisting of R₁₁OH, R₁₂SH, R₁₃R₁₄NH, R₁₆R₁₇NNH₂, and PO(OR₁₅)₃, wherein R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆ and R₁₇ are defined hereinabove to form the desired formula I compound. 